Two-component coating composition based on multi-aspartate esters for producing coatings with good self-healing properties and simultaneously low tack

Abstract

The invention relates to a two-component coating composition comprising a polyaspartic acid ester and a polyurethane prepolymer based on a polyether polyol wherein the ratio of polyol, polyether polyol and polyether polyamine and the functionality gt in the coating composition (excluding auxiliaries, additives and solvents); the invention relates to a composition comprising at least one component selected from the group consisting of 1, 2 and 2 in a specific range, to a method for producing these compositions, to the use thereof in the production of coatings and to the use of these coatings as protective coatings, in particular for objects exposed to (repetitive) mechanical stresses.

Description

[0001] The present invention relates to two-component coating compositions comprising polyaspartic acid esters and polyurethane prepolymers based on polyether polyols, wherein the ratios of polyols, polyether polyols and polyether polyamines and the ratios of components with a functionality > 2 in the coating composition (excluding auxiliaries, additives and solvents) are within specific ranges, and also to methods for preparing these compositions, their use in the preparation of coatings and the use of these coatings as protective coatings, in particular for protective coatings for objects exposed to (repeated) mechanical stress.

[0002] Two-component (2K) coating compositions are already known, which comprise a polyisocyanate component as binder and a reactive component reactive toward isocyanate groups, in particular a polyhydroxy component. They are suitable for producing high-quality coatings which can be designed to be hard, elastic, abrasion-resistant, solvent-resistant and, in particular, weather-resistant.

[0003] In this 2K polyurethane coating technology, certain secondary polyamines containing ester groups have been established in recent years, which, in combination with coating polyisocyanates, are particularly suitable as binders in low-solvent or solvent-free (high-solids) coating compositions and allow the coatings to cure rapidly at low temperatures. These secondary polyamines are so-called polyaspartic acid esters, as described, for example, in EP 0403921. Their use alone or in a mixture with other components reactive toward isocyanate groups in 2K coating compositions is described, for example, in EP 0403921, EP 0639628, EP 0667362, EP 0689881, US Pat. No. 5,214,086, EP 0699696, EP 0596360, EP 0893458, DE 19701835 and US Pat. No. 5,243,012.

[0004] Surfaces of objects exposed to repeated mechanical stresses benefit from self-healing capabilities. Fatigue damage can thus be reduced. If impact stresses are involved, the impact energy needs to be absorbed without causing material failure. The material cannot be brittle, but must be elastic. Elastic materials are characterized by a high elongation at break. At the same time, a low glass transition temperature helps the material not to become brittle even at high impact velocities and to remain elastic (time-temperature superposition principle). Advantageous applications of materials that can withstand repeated impact stresses at high impact velocities are, for example, edge protection of wind turbine blades (English: "Leading Edge Protection").

[0005] Materials with self-healing properties can have the disadvantage of being sticky. This is particularly undesirable in the case of coatings, since all types of particles (such as dust or sand) remain adhered to the coating. This can lead to disadvantageous effects in the respective application, such as higher air resistance or an undesirable tactile feel.

[0006] Therefore, coatings with good self-healing properties and at the same time low adhesion are particularly desirable.

[0007] The present invention reports for the first time the self-healing properties of a coating composition comprising polyaspartic acid esters.

[0008] The object of the present invention is to provide a coating with good self-healing ability and low viscosity at the same time. In the context of the present invention, sufficient self-healing ability is defined as an elongation at break > 40% after self-healing for 24 hours (i.e. stored at 23°C and 50% relative air humidity). It is known that viscosity (English "tack") increases with the decrease of the modulus of the material (CADahlquist, "Adhesion-Fundamentals and Practice-A Report of anInternational Conference held at the University of Nottingham, England 20-22September 1966", Maclaren and Sonst Ltd, London). For the present invention, low viscosity is a storage modulus > 0.7MPa at 23°C and 1Hz (determined by dynamic mechanical analysis). Another object of the present invention is to provide a coating with an elongation at break > 100% in an undamaged state and a glass transition temperature (determined by the maximum tangent δ at 1Hz) < 23°C.

[0009] This object is achieved by a two-component coating composition comprising a polyaspartic acid ester and a polyurethane prepolymer based on a polyether polyol, wherein the proportions of polyol, polyether polyol and polyether polyamine in the coating composition (excluding auxiliaries, additives and solvents) and the proportions of components with a functionality > 2 are within specific ranges.

[0010] WO 2004 / 033517A1, WO 2020 / 016292A1 and WO 2020 / 094689A1 describe coating compositions based on polyaspartic acid esters and polyurethane prepolymers based on polyether polyols. In WO 2004 / 033517A1 and WO 2020 / 016292A1, polyether polyols based on propylene oxide and / or ethylene oxide are mainly used, while WO 2020 / 094689 also describes the use of other polyether polyols, such as polyether polyols based on trimethylene oxide. However, none of these documents discloses a coating composition in which the ratio of polyols, polyether polyols and polyether polyamines and the ratio of components with a functionality > 2 are all within the range specified in claim 1, not to mention the effect obtained by this combination of features.

[0011] WO 2020 / 260578A1 also discloses in the examples section an aspartic acid ester-based coating composition (coating 6) containing a polyether-based allophanate prepolymer as a curing agent. Regardless of the fact that the curing agent is not a polyurethane prepolymer, the proportion of components with a functionality > 2 in the coating composition is clearly too high. As can be seen from Example 35 of the experimental section of the document, the coating does not have sufficient self-healing properties.

[0012] The present invention relates to a two-component coating composition (2K coating composition) comprising

[0013] A) at least one polyaspartate-containing component comprising

[0014] One or more polyaspartic acid esters of general formula (I)

[0015]

[0016] in

[0017] m is an integer > 1, preferably 2,

[0018] X is an m-valent organic radical which optionally contains one or more heteroatoms and which is obtainable by removing primary amino groups from polyamines or polyetheramines having cycloaliphatic, linear aliphatic or araliphatic primary amino groups and a molecular weight of 60 to 6000 g / mol and which may contain further functional groups which are reactive toward isocyanate groups and / or further functional groups which are inert at temperatures up to 100° C., and

[0019] The radicals R1 and R2 are identical or different organic radicals each having 1 to 18 carbon atoms,

[0020] and optionally one or more polyaspartic acid esters of general formula (II)

[0021]

[0022] wherein n is m-1, and X and the groups R1 and R2 are as defined above,

[0023] or consisting thereof, and can be obtained by reacting the following components

[0024] A1) at least one polyamine or polyetherpolyamine of the general formula (III),

[0025]

[0026] Where m and X are as defined above,

[0027] and

[0028] A2) at least one compound of the general formula (IV)

[0029] R1OOC-CH=CH-COOR2 (IV)

[0030] Wherein R1 and R2 are as defined above,

[0031] B) at least one NCO-functional polyurethane prepolymer obtainable by reaction of:

[0032] B1) at least one polyisocyanate and

[0033] B2) at least one polyether polyol having linear ether groups and / or branched ether groups of the following general formulae (V) to (VII):

[0034] -O-(CH2) x -(V), where x=2 to 10, preferably 2 to 6, particularly preferably 2 to 4,

[0035] -O-CR 3 R 4 -CH2-(VI), where R 3 and R 4 are independently of one another and are hydrogen or an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms or an aromatic radical having up to 10 carbon atoms, but in which R 3 or R 4 At least one of the groups is not hydrogen, and

[0036] -O-CR 5 R 6 -CR 7 R 8 -(VII), where R 5 To R 8 are independent of each other, and R 5 and R 7 is hydrogen or an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms, and R 6 and R 8 is an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms, or R 6 and R 8 are linked to each other so as to form a saturated or unsaturated ring having up to 8 carbon atoms which may be substituted by an organic radical,

[0037] B3) optionally at least one polyol different from B2,

[0038] C) optionally one or more components reactive toward isocyanate groups different from A,

[0039] D) optionally one or more isocyanate components different from B, selected from D1) modified polyisocyanates obtainable by reaction of monomeric polyisocyanates with polyols and D2) isocyanate components different from D1,

[0040] E) to E1) optional auxiliaries and / or additives, which do not include those of components E2 and E3,

[0041] - E2) optionally inorganic fillers and / or inorganic pigments,

[0042] and / or

[0043] -E3 optional solvent,

[0044] Among them G x Defined as

[0045] The total amount of the following substances

[0046] a polyetherpolyamine of the formula III incorporated into the polyaspartic acid ester of the polyaspartic acid ester-containing component A,

[0047] - polyether polyol B2 and polyol B3 incorporated into the polyurethane prepolymer B,

[0048] - polyols and polyether polyamines belonging to component C, and

[0049] - polyols incorporated into the modified polyisocyanate D1,

[0050] Based on the total weight of components A to E1,

[0051] And GF is defined as

[0052] The total amount of components A to D with a functionality > 2, based on 1 kg of components A to E1,

[0053] wherein the functionality comprises isocyanate groups and isocyanate-reactive groups,

[0054] And among them it applies:

[0055] i) When component B2 comprises ≤100 to ≥70% by weight of linear ether groups and ≥0 to ≤30% by weight of branched ether groups, based in each case on the total amount of linear and branched ether groups in component B2, then G x is ≥35 to ≤72% by weight, and G F is ≥0 to <0.09 mol / kg, and

[0056] ii) when component B2 comprises ≧0 to <70% by weight of linear ether groups and ≦100 to >30% by weight of branched ether groups, based in each case on the total amount of linear and branched ether groups in component B2, and

[0057] ii1) If G F ≥0 to <0.05 mol / kg, then G x ≥35 to <50% by weight, or

[0058] ii2) If G F ≥0.05 to <0.09 mol / kg, then G X ≥35 to ≤65% by weight.

[0059] For the above-mentioned embodiment i), the following preferred ranges apply:

[0060] Preferably, G x It is ≥35 to ≤72 wt %, and GF is ≥0 to ≤0.08 mol / kg, preferably ≥0 to ≤0.05 mol / kg.

[0061] More preferably, G x It is ≥40 to ≤68 wt %, and GF is ≥0 to <0.09 mol / kg, preferably ≥0 to ≤0.08 mol / kg, more preferably ≥0 to ≤0.05 mol / kg.

[0062] Most preferably, Gx is ≥50 to ≤65 wt %, and G F It is ≥0 to <0.09 mol / kg, preferably ≥0 to ≤0.08 mol / kg, more preferably ≥0 to ≤0.05 mol / kg.

[0063] For the above-mentioned embodiment ii2), the following preferred ranges apply:

[0064] Preferably, GF is ≥0.05 to <0.08 mol / kg, and G x 35 to 65% by weight.

[0065] In the context of the present invention, the term "linear" means "unbranched" and the term "linear aliphatic" means "open-chain aliphatic".

[0066] Thus, linear ether groups are unbranched ether groups, for example ether groups with n-propylene units. This is in contrast to branched ether groups, for example ether groups with isopropylene units. Thus, aliphatic linear groups are aliphatic unbranched groups, for example n-propylene. This is in contrast to aliphatic branched groups, for example isopropylene. Open-chain aliphatic groups are called linear aliphatic groups. These groups can be branched or unbranched.

[0067] The present invention also provides a two-component coating composition composed of components A to E (2K coating composition).

[0068] The amounts of polyether polyol B2 and polyol B3 incorporated into the polyurethane prepolymer B, or the amount of polyol incorporated into the modified polyisocyanate D1, should each be determined as follows:

[0069] When components B and D1 are monomer-free linear compounds, i.e. monomer-free compounds based on non-branched polyether polyols or polyols, this is done according to Flory (PJ Flory, "Molecular Size Distribution in Linear Condensation Polymers", JACS 1936, pp. 1877-1885). When components B and D1 are monomer-free branched compounds, i.e. monomer-free compounds based on branched polyether polyols or polyols, this is done by simulation according to WO 2021 / 055398A1. Compounds that are not monomer-free are determined by calculation from the respective recipes of the manufacturing procedure.

[0070] The content of polyether polyol and polyether amine, based on the total weight of components A1 to E1 in the coating composition, can also be determined by quantitative deuterated decomposition and 1 The H-NMR analysis was determined experimentally. For this purpose, about 100 mg of sample were weighed into a test tube together with about 20 mg of naphthalene internal standard. The decomposition reagent used was 2 ml of deuterated sodium hydroxide in deuterated methanol. The test tube was then flame-sealed and placed in an oven at 150 ° C overnight. The next day, a portion of the solution was transferred to an NMR tube and measured by 1 H NMR (400 MHz, 256 scans) measurements. For quantitative evaluation of the measurement results, the structural units characteristic of the respective polyether are integrated and used to calculate the content. The corresponding proton ratios must be taken into account, and it should be noted that this relates to the structural units / repeating units of the polyether.

[0071] The amount of polyetherpolyamine of formula III incorporated into the polyaspartic acid ester of component A containing polyaspartic acid ester is calculated from the recipe of the manufacturing process (for example: PAE-D230 described in RSC Adv., 2018, 8, 13474 is prepared from 115 g of polyetheramine Jeffamine D230 and 172.18 g of diethyl maleate. The product therefore contains 40% polyetheramine.) This is also taken into account when removing secondary components, for example by distillation.

[0072] Component A containing polyaspartic acid esters

[0073] The at least one polyaspartic acid ester-containing component A preferably comprises one or more polyaspartic acid esters of the general formula (I) and optionally (II), wherein R1 and R2 are identical or different alkyl radicals each having 1 to 18 carbon atoms, preferably identical or different alkyl radicals each having 1 to 8 carbon atoms, most preferably in each case an alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl. Most preferably ethyl.

[0074] The at least one polyaspartic acid ester-containing component A comprises one or more polyaspartic acid esters of the general formula (I) and optionally (II), wherein X represents an organic radical obtained by removing a primary amino group from a corresponding polyamine or polyetheramine having a (cyclo)aliphatic or araliphatic primary amino group, which is selected from the following: all known polyamines or polyetheramines having primary amino groups that conform to the general formula (III). Examples of polyamines include the following compounds: ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2,5-diamino-2,5-dimethylhexane, 1,5-diamino-2-methylpentane ( A, from DuPont), 1,6-diaminohexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane or triaminononane, aliphatic polycyclic polyamines, for example tricyclodecane dimethylamine (TCD diamine) or bis(aminomethyl)norbornane, aminofunctional siloxanes, for example diaminopropylsiloxane G10DAS (from Momentive), amines based on fatty alkyl groups, for example Fentamine from Solvay, dimerized fatty acid diamines, for example Priamine from Croda. Examples of polyether polyamines include: 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, and higher molecular weight polyether polyamines with aliphatically attached primary amino groups, for example the polyether polyamines from Huntsman under the trade name Those that sell by name.

[0075] Preferably, the at least one polyaspartic acid ester-containing component A comprises one or more polyaspartic acid esters of the general formula (I) and optionally (II), wherein X represents an organic radical obtained by removing a primary amino group from one of the polyamines of the general formula (III), wherein m=2 and X is a cyclic hydrocarbon radical having at least one cyclic carbocycle. Examples of diamines which can be used with particular preference are 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA), 2,4- and / or 2,6-hexahydrotoluenediamine (H6-TDA), isopropyl-2,4-diaminocyclohexane and / or isopropyl-2,6-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 2,4′- and / or 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane ( C 260, BASF AG), isomeric diaminodicyclohexylmethanes substituted with methyl groups in the ring (-C-monomethyldiaminodicyclohexylmethane), 3(4)-aminomethyl-1-methylcyclohexylamine (AMCA) and aromatic aliphatic diamines, for example 1,3-bis(aminomethyl)benzene or m-xylylenediamine.

[0076] Likewise preferably, the at least one polyaspartic acid ester-containing component A comprises one or more polyaspartic acid esters of the general formula (I) and optionally (II), in which X represents an organic radical obtained by removing a primary amino group from one of the polyamines or polyetherpolyamines of the general formula (III) selected from the group consisting of polyetherpolyamines with aliphatically attached primary amino groups, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5-diamino- 2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluenediamine, 1,5-diaminopentane, 2,4′- and / or 4,4′-diaminodicyclohexylmethane or 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane. Particular preference is given to 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 1,5-diaminopentane, 2,4′- and / or 4,4′-diaminodicyclohexylmethane, 1,5-diamino-2-methylpentane, and very particular preference is given to using 2,4′- and / or 4,4′-diaminodicyclohexylmethane.

[0077] More preferably, the at least one polyaspartic acid ester-containing component A comprises one or more polyaspartic acid esters of the general formula (I) and optionally (II), wherein X represents an organic radical obtained by removing a primary amino group from a polyamine or polyetherpolyamine of the general formula (III) selected from the group consisting of polyetherpolyamines having aliphatically attached primary amino groups, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 1,2-Diamino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluenediamine, 2,4′- and / or 4,4′-diaminodicyclohexylmethane or 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane.

[0078] The at least one polyaspartic acid ester-containing component A most preferably comprises one or more polyaspartic acid esters of the general formula (I) and optionally (II), in which X represents an organic radical obtained by removing a primary amino group from one of the following polyamines of the general formula (III): 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 2,4′- and / or 4,4′-diaminodicyclohexylmethane, 1,5-diamino-2-methylpentane.

[0079] The index m is an integer >1, preferably 2.

[0080] When the at least one polyaspartic acid ester-containing component A comprises one or more polyaspartic acid esters of the general formula (II), the one or more polyaspartic acid esters of the general formula (II) are contained in a proportion of >0% of the GC area, preferably at least 0.1% (≥0.1%), more preferably at least 1% (≥1%), most preferably at least 4% (≥4%), preferably a maximum of 20% (≤20%), more preferably a maximum of 15% (≤15%) (measured as area % of the gas chromatogram), wherein the sum of the GC areas of the two compounds of the general formulae (I) and (II) is 100%. The indicated upper and lower limits can be combined arbitrarily. All possible combinations are regarded as disclosed.

[0081] The at least one polyaspartic acid ester-containing component A preferably comprises one or more polyaspartic acid esters of the general formula (I) and optionally (II), wherein the platinum-cobalt color index of the esters is ≤200, more preferably ≤100. The platinum-cobalt color index is measured according to DIN EN ISO 6271:2016-05.

[0082] The component A containing polyaspartic acid ester used in the present invention can be prepared by the following method:

[0083] The polyamine or polyether polyamine of general formula (III) is

[0084]

[0085] Where X

[0086] is an m-valent organic radical which optionally contains one or more heteroatoms, which is obtainable by removing primary amino groups from polyamines or polyetheramines having (cyclo)aliphatic or araliphatic primary amino groups and a molecular weight of >60 to ≤6000 g / mol, and which may contain further functional groups which are reactive toward isocyanate groups and / or further functional groups which are inert at temperatures up to 100° C., and

[0087] m is an integer > 1, preferably 2,

[0088] Reaction with a compound of formula (IV)

[0089] R 1 OOC-CH=CH-COOR 2 (IV)

[0090] Where R1 and R2

[0091] are the same or different organic groups, preferably the same or different alkyl groups each having 1 to 18 carbon atoms, more preferably the same or different alkyl groups each having 1 to 8 carbon atoms, most preferably each being an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl, most preferably ethyl,

[0092] The excess proportion of the compound of the general formula (IV) is removed by distillation.

[0093] In the first step, the compounds of the general formula (III) and (IV) are reacted at a temperature of 0°C to 100°C, preferably 20 to 80°C, more preferably 20 to 60°C, wherein the ratio of the equivalents of primary amino groups in the compound of the general formula (III) to the equivalents of C=C double bonds in the compound of the general formula (IV) is 1:1.2 to 1.2:1, preferably 1:1.05 to 1.05:1, more preferably 1:1, until the residual content of the compound of the general formula (IV) is 2 to 15% by weight, preferably 3 to 10% by weight.

[0094] A polyaspartic acid ester-containing component A which contains only polyaspartic acid esters of the general formula (I) but not polyaspartic acid esters of the general formula (II) or contains almost no polyaspartic acid esters of the general formula (II) can be prepared in an analogous manner, but the operation is carried out using an excess of the compound of the general formula (IV), i.e., the ratio of the primary amino group equivalents in the compound of the general formula (III) to the C=C double bond equivalents in the compound of the general formula (IV) is 1:10, preferably 1:5, and more preferably 1:2.

[0095] The reaction is followed by a distillation step in which excess compound of the general formula (IV) is removed.

[0096] Suitable conditions during the distillation are a pressure range of 0.01 to 2 mbar and a temperature of the bottoms stream on leaving the distillation apparatus of ≤170° C. and ≥ the temperature given by the following formula (VIII):

[0097] T(bottom outflow) = 27 x ln(p) + 150(VIII)

[0098] Where T(Bottom effluent) is the temperature of the bottom effluent in °C,

[0099] p is the pressure in the distillation apparatus in millibars.

[0100] By adhering to this pressure range, it is ensured on the one hand that the moderate temperature in the bottom effluent is sufficient to consume the compound of formula (IV) to the desired extent and on the other hand that the process can still be used on an industrial scale. At lower pressures, the gas density becomes too low and the required apparatus is therefore too large, making the process economically disadvantageous.

[0101] The temperature of the bottom effluent is preferably ≤ 170°C, but at least 20K higher than the temperature obtained by formula (VIII); more preferably, 20K to 40K higher than the temperature obtained by formula (VIII), but not higher than 170°C.

[0102] During the preparation of polyaspartic acid esters based on maleic acid esters as compounds of formula (IV), a reverse Michael addition reaction may occur as an undesirable side reaction, wherein the elimination of polyamines leads to the formation of the corresponding dialkyl fumarates as secondary components. This leads to sensitization. These are counted as compounds of formula (IV) and are removed in the distillation step, or their content is significantly reduced by distillation.

[0103] When the polyaspartic acid ester-containing component A comprises dialkyl fumarates, these dialkyl fumarates are contained in an amount of ≥0 to ≤3% by weight, based on the total weight of component A, preferably ≥0.01 to ≤1.5% by weight, more preferably ≥0.01 to ≤1% by weight, most preferably ≥0.01 to ≤0.5% by weight.

[0104] With regard to examples and preferred ranges of polyamines of the general formula (III) which can be used in the above-described process, reference is made to the preceding statements.

[0105] The preferred compound of formula (IV) used in the above method is a maleate or fumarate of formula (IV), wherein R1 and R2 are the same or different organic groups each having 1 to 18 carbon atoms. 2Independently of each other, it is a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably each is an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl, most preferably ethyl. Examples of compounds of general formula (IV) include the following compounds: dimethyl maleate, diethyl maleate, di-n-propyl maleate or diisopropyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate or the corresponding fumarate. Particularly preferred is diethyl maleate.

[0106] Component B

[0107] The two-component coating composition of the invention comprises as component B at least one NCO-functional polyurethane prepolymer which is obtainable by the following reaction:

[0108] B 1) at least one polyisocyanate and

[0109] B2) at least one polyether polyol, and

[0110] B3) Optionally at least one polyol different from B2.

[0111] The functionality of the polyisocyanates B1 suitable for preparing the NCO-functional polyurethane prepolymers is preferably ≥2.

[0112] Polyisocyanates B1 suitable for preparing the NCO-functional polyurethane prepolymers are, for example, monomeric polyisocyanates. These include any monomeric diisocyanates obtainable by phosgenation in the liquid or gas phase or by phosgene-free routes. Preferred diisocyanates are diisocyanates with a molecular weight of 140 to 400 g / mol having linear aliphatic, alicyclic, araliphatic and / or aromatically linked isocyanate groups, for example 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate (PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 2-methyl-1,5-diisocyanatobut ... Isocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Hexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4(3)isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbornane, 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatoprop-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 2,4- and 2,6-diisocyanatotoluene (toluene diisocyanate, TDI), 2,4′- and 4,4′-diisocyanatodiphenylmethane (MDI), 1,5-diisocyanatonaphthalene or a mixture of at least two such diisocyanates. An example of a monomeric polyisocyanate with an NCO functionality >2 is triisocyanatononane (TIN).

[0113] Particularly preferred diisocyanates are diisocyanates with a molecular weight of 140 to 400 g / mol having linear aliphatic, cycloaliphatic and / or araliphatic isocyanate groups, very particularly preferably diisocyanates with linear aliphatic and / or cycloaliphatic isocyanate groups, also preferably diisocyanates with linear aliphatic isocyanate groups. Most preferred are PDI and / or HDI.

[0114] Other polyisocyanates B1 suitable for preparing NCO-functional polyurethane prepolymers are linear aliphatic, alicyclic, araliphatic and aromatic polyisocyanates (hereinafter also referred to as modified polyisocyanates) having an NCO functionality of ≥2 and having uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and / or oxadiazinetriaone structures. These can be obtained from monomeric polyisocyanates having an NCO functionality of ≥2 of the above-mentioned type. Their synthesis is described, for example, in J. Prakt. Chem. 336 (1994) 185-200, DE-A 1670666, DE-A 1954093, DE-A 2414413, DE-A 2452532, DE-A 2641380, DE-A 3700209, DE-A 3900053 and DE-A 3928503 or in EP-A 0336205, EP-A 0339396 and EP-A 0798299 and DE-A 870400, DE-A 953012, DE-A 1090196, EP-A 0546399, CN 105218780, CN 103881050, CN 101717571, US 3183112, EP-A0416338, EP-A 0751163, EP-A1378529, EP-A 1378530, EP-A 2174967, JP 63260915 and JP 56059828.

[0115] In the preparation of these modified polyisocyanates B1, after the actual modification reaction with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and / or oxadiazinetriaone structures, a further process step for separating off the unreacted excess monomeric isocyanate is usually carried out. The monomers are separated off by methods known per se, preferably by thin-film distillation under high vacuum or by extraction with suitable solvents inert to isocyanate groups, such as aliphatic or alicyclic hydrocarbons, such as pentane, hexane, heptane, cyclopentane or cyclohexane. Preferably, the modified polyisocyanates thus obtained have a monomeric isocyanate content of less than 0.5% by weight, more preferably less than 0.3% by weight. The residual monomer content is measured by gas chromatography with an internal standard in accordance with DIN EN ISO 10283:2007-11.

[0116] Preferred modified polyisocyanates B1 are polyisocyanates having an NCO functionality of ≥2 and having a uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and / or oxadiazinedione structure and having only linear aliphatic and / or cycloaliphatic isocyanate groups. Particularly preferred are polyisocyanates having an NCO functionality of ≥2 and having an isocyanurate and / or allophanate structure, which have only linear aliphatic and / or cycloaliphatic isocyanate groups, preferably those based on PDI, HDI, IPDI and / or 4,4′-diisocyanatodicyclohexylmethane. Most preferred are polyisocyanates having an NCO functionality of ≥2 and having an isocyanurate and / or allophanate structure, which have only linear aliphatic isocyanate groups, preferably those based on PDI or HDI.

[0117] In principle, it is of course also possible to use mixtures of different polyisocyanates of the abovementioned type.

[0118] The polyether polyols B2 suitable for preparing NCO-functional polyurethane prepolymers preferably have a number average molecular weight Mn of ≥200 to ≤10 000 g / mol, more preferably ≥400 to ≤2500 g / mol, and an average hydroxyl functionality of preferably ≥1.8 to ≥6, more preferably ≤1.9 to ≤2.1 g / mol, most preferably ≥1.9 to ≤2 g / mol.

[0119] Suitable polyether polyols B2 have linear and / or branched ether groups of the following general formulae (V) to (VII):

[0120] i)-O-(CH2) x -(V), wherein x is 2 to 10, preferably 2 to 6, more preferably 2 to 4,

[0121] ii) O-CR 3 R 4 -CH2-(VI), where R 3 and R 4 are independently of one another and are hydrogen or an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms or an aromatic radical having up to 10 carbon atoms, but in which R 3 or R 4 At least one of the radicals is not hydrogen.

[0122] Preferably, R 3 and R 4 are independently hydrogen or an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms, but in which R 3 or R 4 At least one of the radicals is not hydrogen.

[0123] Particularly preferably, R 3 is hydrogen and R 4 It is an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms, preferably 6 carbon atoms.

[0124] iii) -O-CR 5 R 6 -CR 7 R 8 -(VII), where R 5 To R 8 are independent of each other, and R 5 and R 7 is hydrogen or an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms, and R 6 and R 8 is an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms, or R 6 and R 8 are linked to each other so as to form a saturated or unsaturated ring having up to 8 carbon atoms which may be substituted by an organic group.

[0125] Preferably, R 5 To R 8 are independent of each other, and R 5 and R 7 is hydrogen, and R 6 and R 8 It is an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms, preferably 6 carbon atoms.

[0126] Suitable polyether polyols B2 are obtainable, for example, by ring-opening polymerization of cyclic ethers in the presence of hydroxy-functional compounds.

[0127] Suitable hydroxy-functional compounds are preferably water or compounds with an OH functionality of ≥2 to ≤6, for example propane-1,2-diol, propane-1,3-diol, ethylene glycol, diethylene glycol, dipropylene glycol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, hexanediol, pentanediol, 3-methylpentane-1,5-diol, dodecane-1,12-diol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, catechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, or methylol-containing condensates of formaldehyde and phenol. These can also be used in the form of mixtures. Preference is given to polyols selected from propane-1,2-diol, propane-1,3-diol, glycerol, trimethylolpropane and pentaerythritol.

[0128] Suitable cyclic ethers for preparing the polyether polyols B2 are, for example, the following compounds: ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-butylene oxide (isobutylene oxide), 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butylene oxide, 3-methyl-1,2-butylene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butylene oxide, 1,2-heptane oxide, 1,2-octane oxide, 1,2 - epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 4-methyl-1,2-epoxypentane, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptane oxide, cyclooctane oxide, styrene oxide, methylstyrene oxide, pinene oxide, glycidyl derivatives such as methyl glycidyl ether, ethyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, trimethylene oxide, tetramethylene oxide (THF), pentamethylene oxide, hexamethylene oxide, heptamethylene oxide, decamethylene oxide. Multiple of these ethers may also be copolymerized.

[0129] Preferably, the polyether polyol B2 is based on ethylene oxide, propylene oxide and / or tetramethylene oxide (THF), more preferably on propylene oxide and / or tetramethylene oxide (THF).

[0130] The synthesis of polyether polyols of the above type has been described in detail in, for example, DE 2622951B, column 6, line 65 to column 7, line 26, EP-A0978523, page 4, line 45 to page 5, line 14, WO 2011 / 069966, page 4, line 20 to page 5, line 23. Ring-opening polymerization is known for its synthesis by acid catalysis, for example for the preparation of polyTHF. For a detailed description, see, for example, Angew. Chem. 72, 927 (1960).

[0131] For the preparation of NCO-functional polyurethane prepolymers, it is possible to use further polyols (B3) other than B2.

[0132] These may be, for example, low molecular weight polyols with a molecular weight of 62 to 300 g / mol, such as ethylene glycol, propylene glycol, trimethylolpropane, glycerol or mixtures of these alcohols, or polyols with a molecular weight of more than 300 g / mol, preferably more than 400 g / mol, more preferably from 400 to 20000 g / mol. Such polyols are in particular compounds having 2 to 6 hydroxyl groups, preferably 2 to 3 hydroxyl groups per molecule, and are selected from polyester polyols, polythioether polyols, polyurethane polyols, polycarbonate polyols and polyacrylate polyols.

[0133] For the preparation of the NCO-functional polyurethane prepolymer, the polyisocyanate(s) B1 and the polyether polyol(s) B2 and optionally the polyol(s) B3 are reacted, wherein an NCO / OH equivalent ratio of 1.5:1 to 20:1 is observed to form the urethane. The reaction is carried out at a temperature of 20 to 200° C., preferably 40 to 140° C., more preferably 50 to 120° C. When an excess of more than 2:1 of polyisocyanate is used, the excess monomeric polyisocyanate is preferably removed after the reaction by distillation or extraction methods customary in the prior art, such as thin-film distillation.

[0134] The reaction can be accelerated by using a catalyst which accelerates the formation of carbamates. Examples of conventional catalysts are organotin compounds, bismuth compounds, zinc compounds, titanium compounds, zirconium compounds or amine catalysts. When one or more catalysts are used, the amount of the catalyst or catalyst combination is preferably 0.001 to 5% by weight, in particular 0.002 to 2% by weight, based on the total weight of the prepolymer mixture.

[0135] The reaction can be carried out using a solvent or a solvent mixture. Examples of customary solvents are the solvents described below under "auxiliaries and additives (component E)" for the preparation of the two-component coating composition according to the invention. Reference is made here to the list there.

[0136] The proportion of polyether polyol B2, based on the total weight of component B, is at least 30% by weight, preferably at least 40% by weight, more preferably at least 60% by weight.

[0137] Preferably, the average NCO functionality of the polyurethane prepolymer is >1.8, preferably ≥2 to ≤2.3.

[0138] Component C

[0139] In addition to the polyaspartic acid ester-containing component A, the two-component composition of the invention may also comprise further components which are reactive toward isocyanate groups.

[0140] These may be, for example, low molecular weight polyols having a molecular weight range of 62 to 300 g / mol, such as ethylene glycol, propylene glycol, trimethylolpropane or glycerol.

[0141] They may also be polyols having a molecular weight of greater than 300 g / mol, preferably greater than 400 g / mol, more preferably 400 to 20000 g / mol. Such polyols are in particular polyols having 2 to 6 hydroxyl groups, preferably 2 to 3 hydroxyl groups per molecule, and are selected from polyester polyols, polyether polyols, polythioether polyols, polyurethane polyols, polycarbonate polyols and polyacrylate polyols.

[0142] Useful compounds reactive toward isocyanate groups also include, for example, polyamines or polyetherpolyamines. Particularly suitable polyamines are those having at least two primary and optionally also secondary amino groups per molecule and preferably having an average molecular weight of 60 to 500. Suitable examples are ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, isomeric xylylenediamine, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 1,3-diaminocyclopentane, 4,4′-diaminodicyclohexylsulfone, 4,4′-diamino-1,3-dicyclohexylpropane, 4,4′-diamino-2,2 - dicyclohexylpropane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3-aminomethyl-3,3,5-trimethylcyclohexylamine (isophoronediamine), 3(4)-aminomethyl-1-methylcyclohexylamine, technical-grade bisaminomethyltricyclodecane, octahydro-4,7-methyleneindene-1,5-dimethylamine or polyamines which, in addition to at least two primary amino groups, also have secondary amino groups, such as diethylenetriamine or triethylenetetramine. Particularly suitable polyetherpolyamines are polyetherpolyamines having aliphatically attached primary amino groups, such as those marketed under the trade name TRIAMINE® by Huntsman. The ones that are sold.

[0143] Isocyanate component D

[0144] Suitable isocyanate components D (different from B) are, for example, monomeric polyisocyanates (component D2). For a description of suitable monomeric polyisocyanates, reference is made to the description of monomeric polyisocyanates under component B1. These apply analogously here, including the preferred ranges mentioned above.

[0145] Also suitable as isocyanate component D are modified polyisocyanates, i.e. linear aliphatic, alicyclic, aromatic and aromatic polyisocyanates having an NCO functionality of ≥2 and having uretdione, isocyanurate, carbamate, allophanate, urea, biuret, iminooxadiazinedione and / or oxadiazinetrione structures. These can be obtained from monomeric polyisocyanates having an NCO functionality of ≥2 of the above-mentioned type. Polyisocyanates modified with carbamate and / or allophanate structures are preferably reacted with polyester polyols, polythioether polyols, polyurethane polyols, polycarbonate polyols and / or polyacrylate polyols based on monomeric polyisocyanates, and are included in component D1). Modified polyisocyanates that do not have carbamate and / or allophanate structures are included in component D2).

[0146] With regard to the synthesis and processing of the modified polyisocyanates, please refer to the instructions under component B1. This applies analogously here.

[0147] Preferred modified polyisocyanates are polyisocyanates with an NCO functionality of ≥2 and with a uretdione, isocyanurate, urethane, allophanate, urea, biuret, iminooxadiazinedione and / or oxadiazinedione structure and having only linear aliphatic and / or cycloaliphatic isocyanate groups. Particularly preferred are polyisocyanates with an NCO functionality of ≥2 and with an isocyanurate, urethane and / or allophanate structure, which have only linear aliphatic and / or cycloaliphatic isocyanate groups, preferably polyisocyanates based on PDI, HDI, IPDI and / or 4,4′-diisocyanatodicyclohexylmethane. Most preferred are polyisocyanates with an NCO functionality of ≥2 and with an isocyanurate, urethane and / or allophanate structure, which have only linear aliphatic isocyanate groups, preferably polyisocyanates based on PDI, HDI.

[0148] Components E1 and E2

[0149] E1 includes, for example, organic pigments, fillers or fibers, such as indigo, PTFE particles or Kevlar fibers. Component E2 includes inorganic pigments and fillers, such as titanium dioxide, zinc oxide, iron oxide, chromium oxide, carbon black, barite, chalk, wollastonite or talc. A comprehensive review of pigments and fillers for coatings is given in "Lehrbuch der Lacke und Beschichtungen, Volume 11, Pigmente, Füllstoffe, Farbstoffe", H. Kittel, Verlag WA Colomb in der Heenemann GmbH, Berlin-Oberschwandorf, 1974, pages 17-265.

[0150] Auxiliaries and additives E1 also include catalysts / activators, for example catalysts containing titanium, zirconium, bismuth, tin and / or iron, as described, for example, in WO 05058996. Amines or amidines may also be added.

[0151] Examples of further suitable auxiliaries and additives E1 are coating additives, for example light stabilizers, such as UV absorbers and hindered amines (HALS), and stabilizers, defoamers, anti-cratering agents and / or wetting agents, leveling agents, film-forming aids, reactive diluents, biocides, solvents or rheology control substances. The use of light stabilizers, especially UV absorbers, such as substituted benzotriazoles, S-phenyltriazines or oxalanilides, and hindered amines, especially hindered amines with a 2,2,6,6-tetramethylpiperidinyl structure (known as HALS) is described in A. Valet, Lichtschutzmittel für Lacke, Vincentz Verlag, Hannover, 1996.

[0152] Stabilizers, such as free radical scavengers and other polymerization inhibitors, such as hindered phenols, stabilize the coating composition during storage and are intended to prevent discoloration during the curing process. Wetting agents and leveling agents improve the surface wettability and / or leveling of the coating. Examples are fluorosurfactants, silicone surfactants and specific polyacrylates. Rheology control additives are very important for controlling the properties of two-component systems during application and in the leveling phase on the substrate, as is known, for example, from the patent documents WO 9422968, EP0276501, EP0249201 or WO 9712945. In addition, water scavengers, such as triethyl orthoformate, toluenesulfonyl isocyanate, monooxazolidines or molecular sieves, and hydrolysis stabilizers, such as carbodiimides, can also be used. For a comprehensive review of coating additives, see "Lehrbuch der Lacke und Beschichtungen, Volume 1II, Weichmacher, Additive, Zwischenprodukte", H. Kittel, Verlag WA Colomb in der Heenemann GmbH, Berlin-Oberschwandorf, 1976, pp. 237-398.

[0153] Solvent (E3 component)

[0154] The solvent can be an organic solvent or a mixture of organic solvents. Suitable solvents should be used in a manner and type known to those skilled in the art that matches the composition and the application method. The solvent should dissolve the components used and promote their mixing and avoid incompatibility. In addition, during application and curing, the coating should match the ongoing crosslinking reaction so that a solvent-free coating with a good appearance as much as possible and without defects such as cracks or pinholes is formed. Suitable solvents particularly include solvents for two-component technology. Examples of organic solvents are ketones, such as acetone, methyl ethyl ketone or hexanone, esters, such as ethyl acetate, butyl acetate, methoxypropyl acetate, substituted ethylene glycol and other ethers, aromatic compounds, such as xylene or solvent naphtha, such as from Exxon-Chemie, and mixtures of the solvents. When the NCO reactive part in the composition is in the form of an aqueous dispersion, water is also suitable as a solvent or diluent.

[0155] The molar ratio of the isocyanate groups of B and D to the NCO-reactive groups of A and C in the coating composition is preferably from 0.5:1.0 to 3.0:1.0. A ratio of from 0.9:1.0 to 1.5:1.0 is particularly preferred. A ratio of from 0.99:1.0 to 1.2:1.0 is very particularly preferred.

[0156] If the coating composition comprises a component C reactive toward isocyanate groups other than A, its proportion is not more than 75% by weight, preferably not more than 50% by weight, based on the total weight of components A to E2.

[0157] If the coating composition comprises an isocyanate component D which is different from B, its proportion is a maximum of 50% by weight, preferably a maximum of 30% by weight, based on the total weight of components A to E2.

[0158] When the coating composition comprises auxiliaries and / or additives (component E1) and / or inorganic fillers and / or inorganic pigments (component E2), their proportion is a maximum of 60% by weight, preferably a maximum of 25% by weight, more preferably a maximum of 10% by weight, based on the total weight of components A to E2.

[0159] If solvents (component E3) are contained in the coating composition, their proportion is not more than 50% by weight, preferably not more than 25% by weight, based on the total weight of components A to E3.

[0160] The two-component composition of the invention is preferably not a foamable or foam-forming composition. The composition is preferably not free-radically polymerizable, in particular not photopolymerizable, ie the composition does not cure by a free-radical process, in particular not by a free-radical polymerization process initiated by actinic radiation.

[0161] The two-component coating compositions of the invention are prepared by methods known per se from coatings technology.

[0162] First, the isocyanate-reactive component (R) and the isocyanate-containing component (H) are prepared by mixing the respective isocyanate-reactive components A and C and by mixing the respective polyisocyanate components B and D. Preferably, the auxiliary agent and the additive E are mixed into the isocyanate-reactive component R. The mixing of the components R and H prepared in this way is carried out before or during the application. When mixing before application, it should be noted that the reaction of the ingredients has already started after mixing. Depending on the selection of components and additives, the reaction proceeds at different speeds. The processing time within which the composition must be applied is also called the pot life, which is defined as the time from mixing of the components to doubling of the flow time; depending on the selection of the components, it is 1 minute to 24 hours, usually 10 minutes to 8 hours. The pot life is determined by methods known to those skilled in the art.

[0163] The present invention also relates to a method for preparing a coating on a substrate, which comprises at least the following steps:

[0164] i) applying the above two-component coating composition to at least a portion of the substrate to be coated, and

[0165] ii) curing the coating composition of step i).

[0166] The substrate may have been fully or partially coated with one or more coatings. These coatings may be still uncured or wet, partially cured or fully cured; preferably, the other coatings on the substrate are partially cured or fully cured. Examples of coatings are basecoats, primers, fillers, putties, surfacers or fully painted substrates which are repainted after possible pretreatment (e.g. sanding or plasma activation).

[0167] Two-component coating compositions are used in particular for producing protective coatings, in particular for objects that are exposed to (repeated) mechanical stress, such as rotor blades of wind turbines or helicopters, aircraft wings and ship propellers. The entire surface of such components can be coated here. It is also possible to coat only certain areas of the component surface, such as the leading edge of a rotor blade, aircraft wing or ship propeller.

[0168] Therefore, further preferred subjects of the present invention are the use of the above-described two-component coating compositions for producing coatings on substrates, the above-described methods for coating substrates using these coatings, and the coated substrates themselves obtained in this way.

[0169] The coating composition can be applied by conventional application methods. Examples of application methods are brushing and rolling, roller coating, scraping, dipping and spraying. After the optional ventilation time, the composition of the present invention is cured or dried on the substrate or object. This is carried out according to the conventional methods in the coating technology either under ambient conditions (in terms of temperature and air humidity) or under forced conditions, for example by raising the furnace temperature, using radiation such as infrared or near infrared or microwave radiation, and using dehumidified and / or heated air or other gases. Preferably, no device for forced curing is used here. The coating composition applied is cured at a temperature of, for example, -20 to 100° C., preferably -10 to 80° C., more preferably 0 to 60° C., most preferably 10 to 40° C. Although not preferred, lower curing temperatures can also be used, but this will result in longer curing times.

[0170] It is also possible, although not preferred, to cure the composition at higher temperatures, for example from 80 to 160° C. or higher.

[0171] After the first coating has cured, another coating can be applied and likewise cured.

[0172] The coating produced by the coating composition of the present invention has the following characteristics:

[0173] - elongation at break after 24 hours of self-repair (ie storage at 23° C. and 50% relative humidity) >40%, preferably >60%, more preferably >90%,

[0174] - the elongation at break in the undamaged state (before the self-repair test) is >100%, preferably >300%, more preferably >500%, and

[0175] The glass transition temperature (determined by the maximum tangent at 1 Hz) is <23° C., preferably <0° C., more preferably <−10° C.; when the coating has multiple glass transition temperatures, at least one of them must meet this condition.

[0176] The storage modulus at -23°C and 1 Hz is >0.7 MPa, preferably >0.8 MPa.

[0177] Experimental Section

[0178] method

[0179] Unless stated otherwise, all percentage data are based on weight.

[0180] Unless otherwise stated, the viscosity is determined in accordance with DIN 53019 at a temperature of 23° C. and a shear rate of 50 / s.

[0181] The NCO content is determined volumetrically in accordance with DIN EN ISO 11909.

[0182] The residual diisocyanate content or monomer content is determined in accordance with DIN EN ISO 10283.

[0183] The stress at break and the elongation at break were determined in accordance with DIN 53504:2017-03. The specimens were first stored at 23°C and 50% relative humidity for 24 h. To check the self-healing properties, the tensile bars were placed on a flat base and cut in the middle transversely to the direction of stretching using a razor blade (Martor, Solingen). The cut surfaces were then glued together again by hand with light pressure for 3 seconds. The specimens were then stored at 23°C and 50% relative humidity for 24 h and the stress at break and the elongation at break were re-determined in accordance with DIN 53504:2017-03.

[0184] The dynamic mechanical analysis was performed in shear mode on a Mettler DMA SDTA 861. Two cylinders with a diameter of 6 mm were inserted into the double shear sample holder. The maximum force amplitude was 0.5 N and the maximum elongation was 2 μm. The measurements were carried out in a temperature range of -100 ° C to +150 ° C, with a heating rate of 1 K / min and test frequencies of 1, 10, 100 and 500 Hz.

[0185] The polyether polyol content of the monomer-free linear prepolymers 1 to 10 was calculated according to Flory (PJ Flory, "Molecular Size Distribution in Linear Condensation Polymers", JACS 1936, pp. 1877-1885). The polyether polyol content of the undistilled prepolymer (prepolymer 11) was calculated simply by means of the respective recipe. The polyether polyol content of the monomer-free branched prepolymer (e.g. Desmodur E30600) was calculated by simulation according to WO 2021 / 055398A1.

[0186] G x It is calculated based on the prepolymer ratio and the predetermined polyether polyol content in the prepolymer. If the aspartic acid ester component A or components C or D contain polyethers, these must also be taken into account.

[0187] The ability of the coating composition to form a tight network is measured by G F to describe.

[0188] Calculate G based on coating material 16 x Example

[0189] As shown in Table 1, coating material 16 contained 63.42 g of prepolymer 7, 13.02 g of Desmodur N 3600, and 43.55 g of Desmophen NH 1420. The total mass was 119.99 g.

[0190] The formulation of prepolymer 7 contained 1680 g HDI and 1000 g polyether Desmophen 1110BD. Therefore, the polyether content of the prepolymer before distillation was 37.3%. According to the Schulz-Flory distribution, 50.8% of the mixture was unreacted monomeric HDI. After distilling off the excess monomeric HDI, the polyether content increased to 75.8%.

[0191] 75.8% of the 63.42 g of prepolymer 7 corresponds to 48.07 g of polyether. Since Desmodur N3600 and Desmophen NH 1420 do not contain polyether, the percentage proportion of polyether based on the total mass of components AD is 100 x 48.07 / 119.99 = 40%. x is 40%.

[0192] Calculate G based on coating material 16 F Example

[0193] As shown in Table 1, coating material 16 contained 63.42 g of prepolymer 7, 13.02 g of Desmodur N 3600, and 43.55 g of Desmophen NH 1420. The total mass was 119.99 g.

[0194] The functionality of prepolymer 7 and Desmophen NH 1420 is 2. The functionality of Desmodur N 3600 is >2 and the number average molecular weight Mn is 710 g / mol. Therefore, 13.02 g of Desmodur N3600 corresponds to 0.018 mol in 119.99 g. Based on 1 kg of component AD, this molar amount is 0.15 mol. Therefore, G F It is 0.15mol / kg.

[0195] Substances used and abbreviations

[0196] HDI: Hexamethylene diisocyanate ( H, Covestro Deutschland AG)

[0197] Poly(tetrahydrofuran): Products with number average molar masses of 250, 1000, 1400, and 2000 g / mol were purchased from BASF. Poly(tetrahydrofuran) with a number average molar mass of 650 g / mol was provided by Merck.

[0198] N 3600: product of Covestro Deutschland AG, HDI isocyanurate trimer, functionality>2, NCO content 23%, average molar mass 710 g / mol (determined by GPC).

[0199] E30600: a product of Covestro Deutschland AG, an HDI prepolymer based on polypropylene glycol, functionality>2, a polyol content of 75.6%, and an average molar mass of 2755 g / mol (determined by GPC).

[0200] 1262BD: Product of Covestro Deutschland AG, difunctional polypropylene glycol, average molar mass 431.5 g / mol (OH value 260 mg KOH / g)

[0201] 1110BD: Product of Covestro Deutschland AG, difunctional polypropylene glycol, average molar mass 1000 g / mol (OH value 112 mg KOH / g)

[0202] 2060BD: Product of Covestro Deutschland AG, difunctional polypropylene glycol, average molar mass 2000 g / mol (OH value 56 mg KOH / g)

[0203] 1000H: Product of SK Chemicals, difunctional poly(propane-1,3-diol), average molar mass 1000 g / mol (OH value 112 mg KOH / g)

[0204] NH 1420: Product of Covestro Deutschland AG, difunctional amine, equivalent weight 276 g / mol, free of polyether groups.

[0205] Prepolymer 1

[0206] 1680 g HDI was pre-loaded, heated to 80 ° C, and 250 g of poly (tetrahydrofuran) with an average molar mass of 250 g / mol (OH value 450 mg KOH / g) was added dropwise within 60 minutes under stirring. Stir for another 120 minutes at 80 ° C until the NCO content reached 38.6%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130 ° C, main evaporator 120 ° C) and under a vacuum of 0.08 mbar. A prepolymer was obtained, which solidified into a white solid when cooled to room temperature. The following properties were obtained:

[0207] NCO content: 13.4%

[0208] Residual monomer content: 0.08%

[0209] Viscosity at 50°C: 185mPas

[0210] Polyether polyol content (calculated value): 43.9%

[0211] Functionality: 2

[0212] Prepolymer 2

[0213] 1680 g of HDI were pre-loaded, heated to 80° C., and 650 g of poly(tetrahydrofuran) (OH value 173 mg KOH / g) with an average molar mass of 650 g / mol was added dropwise over 60 minutes under stirring. Stirring was continued at 80° C. for another 190 minutes until the NCO content reached 32.2%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130° C., main evaporator 120° C.) and under a vacuum of 0.04 mbar. A liquid prepolymer with the following properties was obtained:

[0214] NCO content: 7.6%

[0215] Residual monomer content: 0.04%

[0216] Viscosity: 1610mPas

[0217] Polyether polyol content (calculated value): 67.0%

[0218] Functionality: 2

[0219] Prepolymer 3

[0220] 2520 g of HDI were pre-loaded, heated to 80 ° C, and 1500 g of poly(tetrahydrofuran) (OH value 112 mgKOH / g) with an average molar mass of 1000 g / mol was added dropwise under stirring within 60 minutes. Stirring was continued at 80 ° C for 75 minutes until the NCO content reached 27.9%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130 ° C, main evaporator 120 ° C) and under a vacuum of 0.04 mbar. A liquid prepolymer was initially obtained, which slowly solidified into a white solid after a few days. The following properties were measured:

[0221] NCO content: 5.7%

[0222] Residual monomer content: 0.04%

[0223] Viscosity: 2200mPas

[0224] Polyether polyol content (calculated value): 75.8%

[0225] Functionality: 2

[0226] Prepolymer 4

[0227] 840 g of HDI were pre-loaded, heated to 80 ° C, and 700 g of poly(tetrahydrofuran) with an average molar mass of 1400 g / mol (OH value 80 mg KOH / g) were added dropwise over 60 minutes under stirring. Stirring was continued at 80 ° C for another 120 minutes until the NCO content reached 24.3%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130 ° C, main evaporator 120 ° C) and under a vacuum of 0.04 mbar. A liquid prepolymer was initially obtained, which slowly solidified into a white solid within a few days. The following properties were measured:

[0228] NCO content: 4.4%

[0229] Residual monomer content: 0.03%

[0230] Viscosity: 4780mPas

[0231] Polyether polyol content (calculated value): 81.4%

[0232] Functionality: 2

[0233] Prepolymer 5

[0234] 630 g of HDI were pre-loaded, heated to 80 ° C, and 750 g of poly(tetrahydrofuran) (OH value 56 mgKOH / g) with an average molar mass of 2000 g / mol was added dropwise under stirring within 105 minutes. Stirring was continued at 80 ° C for another 250 minutes until the NCO content reached 20.5%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130 ° C, main evaporator 120 ° C) and under a vacuum of 0.1 mbar. A liquid prepolymer was initially obtained, which solidified into a white solid overnight. The following properties were measured:

[0235] NCO content: 3.2%

[0236] Residual monomer content: 0.02%

[0237] Viscosity at 40°C: 2630 mPas

[0238] Polyether polyol content (calculated value): 86.2%

[0239] Functionality: 2

[0240] Prepolymer 6a

[0241] 1680 g of HDI were pre-charged, heated to 80° C., and 431.5 g of Desmophen 1262BD (OH value 260 mg KOH / g) with an average molar mass of 431.5 g / mol were added dropwise over 60 minutes under stirring. Stirring was continued at 80° C. for a further 75 minutes until the NCO content reached 35.7%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130° C., main evaporator 120° C.) and under a vacuum of 0.3 mbar. A liquid prepolymer was obtained.

[0242] NCO content: 10.3%

[0243] Residual monomer content: 0.13%

[0244] Viscosity: 1730mPas

[0245] Polyether polyol content (calculated value): 57.5%

[0246] Functionality: 2

[0247] Prepolymer 6b

[0248] 2520 g of HDI were pre-charged, heated to 80° C., and 647.3 g of Desmophen 1262BD (OH number 260 mg KOH / g) with an average molar mass of 431.5 g / mol were added dropwise over 60 minutes under stirring. Stirring was continued at 80° C. for a further 780 minutes until the NCO content reached 35.8%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130° C., main evaporator 120° C.) under a vacuum of 0.4 mbar. A liquid prepolymer was obtained.

[0249] NCO content: 10.5%

[0250] Residual monomer content: 0.78%

[0251] Viscosity: 1610mPas

[0252] Polyether polyol content (calculated value): 57.0%

[0253] Functionality: 2

[0254] Prepolymer 7

[0255] 1680 g of HDI were pre-charged, heated to 80° C., and 1000 g of Desmophen 1110BD (OH value 112 mg KOH / g) with an average molar mass of 1000 g / mol were added dropwise over 90 minutes under stirring. Stirring was continued at 80° C. for a further 260 minutes until an NCO content of 28.0% was reached. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130° C., main evaporator 120° C.) under a vacuum of 0.08 mbar. A liquid prepolymer was obtained.

[0256] NCO content: 5.9%

[0257] Residual monomer content: 0.04%

[0258] Viscosity: 1500mPas

[0259] Polyether polyol content (calculated value): 75.8%

[0260] Functionality: 2

[0261] Prepolymer 8

[0262] 840 g of HDI were pre-charged, heated to 80° C., and 1000 g of Desmophen 2060BD (OH value 56 mg KOH / g) with an average molar mass of 2000 g / mol was added dropwise over 90 minutes under stirring. Stirring was continued at 80° C. for another 600 minutes until the NCO content reached 20.5%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130° C., main evaporator 120° C.) under a vacuum of 0.04 mbar. A liquid prepolymer was obtained.

[0263] NCO content: 3.3%

[0264] Residual monomer content: 0.03%

[0265] Viscosity: 1530mPas

[0266] Polyether polyol content (calculated value): 86.2%

[0267] Functionality: 2

[0268] Prepolymer 9

[0269] 1680 g of HDI were pre-loaded, heated to 80° C., and 1000 g of Ecoprol H1000 (OH value 56 mgKOH / g) with an average molar mass of 2000 g / mol was added dropwise over 120 minutes under stirring. Stirring was continued at 80° C. for another 150 minutes until the NCO content reached 28.0%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130° C., main evaporator 120° C.) and under a vacuum of 0.08 mbar. A liquid prepolymer was obtained.

[0270] NCO content: 5.8%

[0271] Residual monomer content: 0.07%

[0272] Viscosity: 1670mPas

[0273] Polyether polyol content (calculated value): 75.8%

[0274] Functionality: 2

[0275] Prepolymer 10

[0276] 840 g of HDI were pre-loaded, heated to 80° C., and 1000 g of Ecoprol H2000 (OH value 56 mgKOH / g) with an average molar mass of 2000 g / mol was added dropwise over 60 minutes under stirring. Stirring was continued at 80° C. for another 284 minutes until the NCO content reached 20.5%. Excess HDI was removed in a two-stage short-path evaporator (pre-evaporator 130° C., main evaporator 120° C.) and under a vacuum of 0.04 mbar. A liquid prepolymer was obtained.

[0277] NCO content: 3.3%

[0278] Residual monomer content: 0.07%

[0279] Viscosity: 4520mPas

[0280] Polyether polyol content (calculated value): 86.2%

[0281] Functionality: 2

[0282] Prepolymer 11

[0283] The synthesis was carried out according to Example 3 of US20040067315.

[0284] NCO content: 1.8%

[0285] Viscosity: 13900mPas

[0286] Polyether polyol content (calculated value): 90.0%

[0287] Concentration of components with F>2: 0.045 mol / kg

[0288]

[0289]

[0290]

[0291]

[0292] Embodiment 35

[0293] Coating material according to WO2020 / 260578 A1 coating 6.

[0294] Embodiment 36

[0295] Pigmented coating compositions were prepared according to the formulations in Table 2. For this purpose, component A was prepared in a dissolver (Dispermat, VMA-Getzmann) and then mixed for 1 minute in a Speedmixer (Hausschild DAC 150FVZ) after initial charging with the isocyanate prepolymer (component B).

[0296] Table 2: Preparation of pigmented coating materials

[0297] Embodiment 36 Prepolymer (component B) 3 52.88 Component A Desmophen NH 1220 9.07 Desmophen NH 1420 7.66 Disperbyk 110 0.66 Pure R 706 Titanium Dioxide 24.39 Colour Black FW 200 0.07 BYK 327 0.27 BYK 331 0.14 BYK 1799 1.41 Tinuvin 292 0.63 4A molecular sieve 2.82 Total needle 100 NCO / NH 1.05

[0298] Film preparation

[0299] The coating materials in Examples 1-36 were poured into a mold. Films of about 5 mm thickness were prepared for self-healing tests and films of about 3 mm thickness were used for dynamic mechanical analysis. The films were cured at room temperature for at least 14 days.

[0300] Table 3 summarizes the film properties.

[0301] Rain erosion test

[0302] A 45 cm long U-shaped NACA 63-021 test substrate for simulating the wind edge of a wind turbine rotor blade (English "Leading Edge", as described in Appendix A.1, DNGVL-RP-0171) was first coated with a thin layer of adhesion primer. Then 400 μm of coating composition Example 36 (Table 2) were applied. The coating was cured at room temperature for at least 14 days.

[0303] Rain erosion tests were carried out according to DNVGL-RP 0171, with a rotor speed of 1000 rpm, a water volume flow of 65 L / h, a rain intensity of 31.34 mm / h, an average droplet size of 2.511 mm, and a test chamber temperature of 14 to 23 ° C. The inspection interval was 15 minutes. Even after 20 hours of testing, there was no erosion damage to the coating.

[0304]

[0305]

[0306] Table 3 shows the film properties of films prepared from coating materials 1-35. Examples 1-9 and 36 show coatings containing poly(tetrahydrofuran). Sufficient self-healing properties are only observed when the poly(tetrahydrofuran) content is 35% to 72%. Example 36 also shows rain erosion resistance of at least 20 hours. Examples 7 to 9 were prepared at different NCO: NH ratios of 0.95, 1.05 and 1.15, and show that this task can be accomplished by different NCO: NH ratios. Examples 10-22 and 32-35 show coatings containing poly(propylene glycol). Similar to poly(tetrahydrofuran), coatings with a poly(propylene glycol) content of less than 35% do not show self-healing properties (see Examples 10 and 22). In contrast to poly(tetrahydrofuran), coatings containing poly(propylene glycol) can exhibit self-healing properties even at very high poly(propylene glycol) contents (see Examples 17, 32, 33), but these coatings exhibit high viscosity at this time. Example 32 was carried out according to US20040067315 Table 1 Item 9. The very low storage modulus confirms the increased adhesion. Weakly crosslinked coating (G F = 0 to < 0.05 mol / kg) becomes too viscous at poly(propylene glycol) contents of 50% and above, i.e., the storage modulus is 0.7 or less. This can be partially compensated by crosslinking (see Examples 15 and 19, where G F ≥0.05). However, if there is too much crosslinking, the self-healing properties are lost (see Examples 16, 20, 21, 34, 35). Example 35 was carried out according to coating 6 of WO20260578. Examples 23 to 31 show coatings containing poly(propane-1,3-diol). Similar to the coating material containing poly(tetrahydrofuran), the coating material containing poly(propane-1,3-diol) in G X ≥35% to ≤72% and G F The self-healing performance is shown in the range of <0.09mol / kg.

Claims

1. The subject of the present invention is a two-component coating composition comprising A) at least one polyaspartate-containing component comprising One or more polyaspartic acid esters of general formula (I) in m is an integer > 1, preferably 2, X is an m-valent organic radical which optionally contains one or more heteroatoms and which is obtainable by removing primary amino groups from polyamines or polyetheramines having cycloaliphatic, linear aliphatic or araliphatic primary amino groups and a molecular weight of 60 to 6000 g / mol and which may contain further functional groups which are reactive toward isocyanate groups and / or further functional groups which are inert at temperatures up to 100° C., and The radicals R1 and R2 are identical or different organic radicals each having 1 to 18 carbon atoms, and optionally one or more polyaspartic acid esters of general formula (II) wherein n is m-1, and X and the groups R1 and R2 are as defined above, or consisting thereof, and can be obtained by reacting the following components A1) at least one polyamine or polyetherpolyamine of the general formula (III), Where m and X are as defined above, and A2) at least one compound of the general formula (IV) R1OOC-CH=CH-COOR2 (IV) Wherein R1 and R2 are as defined above, B) at least one NCO-functional polyurethane prepolymer obtainable by reaction of: B1) at least one polyisocyanate and B2) at least one polyether polyol having linear ether groups and / or branched ether groups of the following general formulae (V) to (VII): ─O─(CH2) x ─ (V), where x = 2 to 10, ─O─CR 3 R 4 ─CH2─ (VI), where R 3 and R 4 are independently of one another and are hydrogen or an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms or an aromatic radical having up to 10 carbon atoms, but in which R 3 or R 4 At least one of the groups is not hydrogen, and ─O─CR 5 R 6 ─CR 7 R 8 ─ (VII), where R 5 To R 8 are independent of each other, and R 5 and R 7 is hydrogen or an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms, and R 6 and R 8 is an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms and which may also contain oxygen atoms, or R 6 and R 8 are linked to each other so as to form a saturated or unsaturated ring having up to 8 carbon atoms which may be substituted by an organic radical, B3) optionally at least one polyol different from B2, C) optionally one or more components reactive toward isocyanate groups different from A, D) optionally one or more isocyanate components D different from B, selected from D1) modified polyisocyanates obtained by reacting monomeric polyisocyanates with polyols and D2) other isocyanate components different from D1, E) to E1) optional auxiliaries and / or additives, which do not include those of components E2 and E3, - E2) optionally inorganic fillers and / or inorganic pigments, and / or -E3 optional solvent, Among them G x Defined as The total amount of the following substances a polyetherpolyamine of the formula III incorporated into the polyaspartic acid ester of the polyaspartic acid ester-containing component A, - polyether polyol B2 and polyol B3 incorporated into the polyurethane prepolymer B, - polyols and polyether polyamines belonging to component C, and - polyols incorporated into the modified polyisocyanate D1, Based on the total weight of components A to E1, And G F Defined as The total amount of components A to D with a functionality > 2, based on 1 kg of components A to E1, wherein the functionality comprises isocyanate groups and isocyanate-reactive groups, And among them it applies: i) When component B2 comprises ≤100 to ≥70% by weight of linear ether groups and ≥0 to ≤30% by weight of branched ether groups, based in each case on the total amount of linear and branched ether groups in component B2, then G x is ≥35 to ≤72% by weight, and G F is ≥0 to <0.09 mol / kg, and ii) when component B2 comprises ≧0 to <70% by weight of linear ether groups and ≦100 to >30% by weight of branched ether groups, based in each case on the total amount of linear and branched ether groups in component B2, and ii1) If G F ≥0 to <0.05 mol / kg, then G X ≥35 to <50% by weight, or ii2) If G F ≥0.05 to <0.09 mol / kg, then G X ≥35 to ≤65% by weight.

2. The two-component coating composition according to claim 1, wherein: Component B2 comprises ≤100 to ≥70% by weight of linear ether groups and ≥0 to ≤30% by weight of branched ether groups, based in each case on the total amount of linear and branched ether groups in component B2, and G x ≥35 to ≤72% by weight, G F ≥0 to <0.09 mol / kg.

3. The two-component coating composition according to claim 1, wherein for embodiment i) it is applicable that: G x is ≥35 to ≤72% by weight, and G F It is ≥0 to ≤0.08 mol / kg, preferably ≥0 to ≤0.05 mol / kg.

4. The two-component coating composition according to claim 1, wherein for embodiment i) it is applicable that: G x is ≥40 to ≤68 wt%, and G F It is ≥0 to <0.09 mol / kg, preferably ≥0 to ≤0.08 mol / kg, more preferably ≥0 to ≤0.05 mol / kg.

5. The two-component coating composition according to claim 1, wherein for embodiment ii2) it is applicable: G F is ≥0.05 to <0.08 mol / kg and G X 35 to 65% by weight.

6. A two-component coating composition according to any one of claims 1 to 5, wherein the at least one polyisocyanate B1 is selected from monomeric diisocyanates having linear aliphatic, cycloaliphatic, araliphatic and / or aromatically bonded isocyanate groups and having a molecular weight in the range of 140 to 400 g / mol, and polyisocyanates having a uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and / or oxadiazinedione structure and having an NCO functionality of ≥2 having linear aliphatic, cycloaliphatic, araliphatic and / or aromatically bonded isocyanate groups.

7. The two-component coating composition according to any one of claims 1 to 5, wherein the at least one polyisocyanate B1 is selected from monomeric diisocyanates having exclusively linear aliphatically and / or cycloaliphatically linked isocyanate groups and having a molecular weight in the range of 140 to 400 g / mol.

8. The two-component coating composition according to any one of claims 1 to 7, wherein x in formula (V) is 2 to 6, preferably 2 to 4.

9. The two-component coating composition according to any one of claims 1 to 8, wherein for formula (VI) the following applies: R 3 is hydrogen and R 4 is an aliphatic linear or branched, saturated or unsaturated radical having up to 10 carbon atoms.

10. The two-component coating composition according to any one of claims 1 to 8, wherein for formula (VI) the following applies: R 3 is hydrogen and R 4 is an aliphatic linear or branched saturated radical having up to 6 carbon atoms, preferably methyl.

11. A method for preparing a coating on a substrate, comprising at least the following steps: i) applying the two-component coating composition according to any one of claims 1 to 10 to at least a portion of the substrate to be coated, and ii) curing the coating composition of step i).

12. Substrate coated with a coating obtainable by the process as claimed in claim 11.

13. The method for preparing a coating on a substrate according to claim 11, or the substrate coated with a coating according to claim 12, characterized in that: The coating is a protective coating for objects exposed to mechanical stress.

14. The method for preparing a coating on a substrate according to claim 11 or 13, or the substrate coated with a coating according to claim 12 or 13, characterized in that: The coating is a coating for a rotor blade of a wind turbine or a helicopter, for an airplane wing or a ship propeller.

15. Use of the two-component coating composition according to any one of claims 1 to 10 for producing a coating on a substrate.

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